Smoking compositions containing acylpyrazine ether flavorants

ABSTRACT

In one of its embodiments the present invention provides a smoking composition which contains a novel type of acylpyrazine ether flavorant additive as exemplified by 1-(3-methoxy-2-pyrazinyl)-2-methyl-1-propanone. ##STR1##

BACKGROUND OF THE INVENTION

Alkylpyrazines are typical of organic compounds which have beenrecognized as having useful properties for application as flavorants intobacco and foodstuffs. Various species have been identified in naturalproducts as flavorant or fragrance constituents.

Unlike alkylpyrazines which are ubiquitous in nature and heat-treatedfoodstuffs, acylpyrazines are more limited in their occurrence Forexample, 2-acetyl-5-methylpyrazine and 2-acetyl-5-ethylpyrazine arereported as constituents of cocoa in Tobacco International, page 18ff(March 1979), and 1-(2-pyrazinyl)-1-butanone is tentatively identifiedas a water-soluble component of cigarette smoke in J. Agric. Food Chem.,25(2), 310 (1977).

Several acetylpyrazines are included in the F.E.M.A. listing of foodadditives as being useful for imparting a popcorn-nutty flavor to afoodstuff. The incorporation of acetylpyrazine,2-acetyl-5-methylpyrazine or 2-acetyl-6-methylpyrazine as a popcorn-likeflavorant in foodstuffs and tobacco is described in U.S. Pat. No.3,402,051.

Interest in pyrazines as flavorants or fragrances has stimulated theinvestigation of various types of substituted pyrazines whichpotentially have unique organoleptic properties.

Pyrazine flavorants characterized by the presence of an ethersubstituent are disclosed in U.S. Pat. Nos. 3,622,346; 3,702,253;3,767,425; and 4,105,661.

Methoxy-substituted acetylpyrazines are reported in J. Agric. FoodChem., 23, 638(1975).

U.S. Pat. No. 4,064,124 describes a process for the manufacture of abroad variety of pyrazine derivatives via the reaction of nitrooxiraneswith ammonia.

There is continuing research effort to develop new species of pyrazinetype heterocyclic compounds which exhibit useful flavorant or fragranceproperties.

Accordingly, it is an object of this invention to provide a novel classof acylpyrazine ether compounds which exhibit unique properties forapplication as flavorants. It is another object of this invention toprovide a process for

producing novel acylpyrazine ether compounds.

It is a further object of this invention to provide smoking compositionsof tobacco and non-tobacco materials containing an acylpyrazine etherflavorant additive, which smoking compositions are adapted to impartflavor and aroma to mainstream and sidestream smoke under smokingconditions.

Other objects and advantages of the present invention shall becomeapparent from the accompanying description and examples.

DESCRIPTION OF THE INVENTION

One or more objects of the present invention are accomplished by theprovision of a smoking composition comprising an admixture of (1)combustible filler selected from natural tobacco, reconstituted tobacco,non-tobacco substitutes, and mixtures thereof, and (2) between about0.00001 and 2 weight percent, based on the total weight of filler, of anacylpyrazine ether corresponding to the formula: ##STR2## where R is asubstituent selected from aliphatic, alicyclic and aromatic groupscontaining between about 2-12 carbon atoms, R¹ is a substituent selectedfrom hydrogen and alkyl groups containing between about 1-6 carbonatoms, X is etheric oxygen or sulfur, and R² is a substituent selectedfrom aliphatic, alicyclic and aromatic groups containing between about1-12 carbon atoms, with the proviso that the position-(3) substituent isnot hydrogen.

Illustrative of the R substituent in the represented acylpyrazine etherformula are groups which include ethyl, propyl, propanyl, butyl, pentyl,hexyl, methoxyethyl, ethoxyethyl, cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, menthyl, furyl, tetrahydrofuryl, phenyl, tolyl, xylyl,benzyl, phenylethyl, methoxyphenyl, pyridyl, pyrazyl, and the like.

Illustrative of the R¹ substituents in the represented acylpyrazineether formula are groups which include methyl, ethyl, butyl, isobutyl,pentyl, hexyl, and the like.

Illustrative of the R² substituents in the represented acylpyrazineether formula are groups which include methyl, propyl, butenyl, butynyl,heptyl, ethoxyethyl, cyclopentyl, cyclohexenyl, furfuryl, menthyl,phenyl, benzyl, naphthyl, pyridyl, pyrazyl, and the like.

PREPARATION OF ACYLPYRAZINE ETHERS

Various specific methods of synthesizing acylpyrazine derivatives aredisclosed in patents such as U.S. Pat. Nos. 3,711,482; 3,767,428;3,890,320; and 3,914,227; and the like.

In J. Chem. Soc., Perkin II, 2035 (1972) there is reported the acylationof protonated pyrazine derivatives. In general procedure, aheteroaromatic compound (e.g., pyrazine) is acylated by reacting thecompound with alkanal in the presence of t-butyl hydroperoxide andiron(II) sulfate in a homogeneous aqueous medium of acetic acid andsulfuric acid. Related procedures are disclosed in J. Chem. Soc.(C),229(1970).

In another embodiment, the present invention provides an efficientmethod for the preparation of novel acylpyrazine ethers which involvesthe steps of (1) providing a heterogeneous reaction medium consisting ofa water-immiscible organic phase and an acidic aqueous phase, whereinthe organic phase comprises a mixture of a R--CHO aldehyde compound anda halopyrazine compound corresponding to the formula: ##STR3## where Yis a halogen atom, and R¹ is a substituent selected from hydrogen andalkyl groups containing between about 1-6 carbon atoms, and R in thealdehyde compound is a substituent selected from aliphatic, alicyclicand aromatic groups containing between about 2-12 carbon atoms; (2)maintaining efficient contact between the organic and aqueous phases fora period of time sufficient to achieve acylation of the halopyrazinecompound in the presence of a free radical generating agent; (3)recovering a halo-acylpyrazine intermediate corresponding to theformula: ##STR4## where Y is a halogen atom, R is a substituent selectedfrom aliphatic, alicyclic and aromatic groups containing between about2-12 carbon atoms, and R¹ is a substituent selected from hydrogen andalkyl groups containing between about 1-6 carbon atoms, with the provisothat the position-(2) substituent is not hydrogen; and (4) reacting thehaloacylpyrazine intermediate with a R² --X--M alcoholate, where M is analkali metal atom (e.g., sodium, potassium or lithium), in a liquidmedium under conditions that yield an acylpyrazine ether correspondingto the formula: ##STR5## where R is a substituent selected fromaliphatic, alicyclic and aromatic groups containing between about 2-12carbon atoms, R¹ is a substituent selected from hydrogen and alkylgroups containing between about 1-6 carbon atoms, X is etheric oxygen orsulfur, and R² is a substituent selected from aliphatic, alicyclic andaromatic groups containing between about 1-12 carbon atoms, with theproviso that the position-(3) substituent is not hydrogen.

R, R¹ and R² are substituents of the type previously illustratedhereinabove. Y is a halogen atom such as chlorine, bromine or iodine.

The aldehyde (R--CHO) reactant in step (1) can be any compound whichdoes not contain a substituent which inhibits or prevents the freeradical interaction of the aldehyde functionality with the pyrazinenucleus. It is preferred that the aldehyde reactant is at leastpartially soluble in the aqueous phase of the acylation system, in orderto increase the rate and efficiency of the acylation reaction.

The halopyrazine and aldehyde reactants can be employed over a widerange of molar ratios. It has been found convenient and advantageous toemploy a molar ratio between about 0.5-10:1 of aldehyde to halopyrazinein the acylation system.

The relative volumes of the respective immiscible phases in theacylation system are not critical, and typically the two phases will beapproximately equal in volume.

The acidity of the aqueous phase is provided by the addition of asuitable acid reagent such as sulfuric acid, hydrochloric acid,phosphoric acid, and the like. The pH of the aqueous phase is belowabout 6, and preferably is in the range between about 1-5.

The organic phase usually will comprise a mixture of the pyrazine andaldehyde reactants. If the water-solubility of the halopyrazine andaldehyde reactants are at a sufficiently high level to prevent themaintenance of separate organic and aqueous phases, then suitablemodification of the acylation system is required to accomplish theseparation of phases. Cooling of the acylation system is one means ofproviding the desired phase separation, particularly in combination withother means such as salting of the aqueous phase. A preferredalternative is to include a water-immiscible solvent in the system, suchas hexane, benzene or toluene, since it provides additional advantagessuch as higher product yield and more efficient product recovery.

The acylation reaction between the halopyrazine and aldehyde reactantsis catalyzed by the inclusion of a free radical generating agent, in aquantity between about 1-50 weight percent, based on the weight ofaldehyde reactant.

Illustrative of suitable free radical initiators are hydrogen peroxide;alkali metal or ammonium persulfates, perborates, peracetates andpercarbonates; organic peroxides and hydroperoxides such as benzoylperoxide, t-butyl hydroperoxide and diisopropylperoxydicarbonate; andthe like. The initiator may be associated with activating means (e.g., aredox system) which involves the use of compounds such as sulfites andthiosulfites, and redox reaction promoters such as transition metal ions(e.g., Fe⁺⁺).

The step (4) nucleophilic reaction, which introduces an ethericsubstituent in place of a halogen substituent in the pyrazine ring,proceeds readily in a solvent medium (e.g., ethanol) at 0°-60° C.employing approximately equimolar proportions of halo-acylpyrazine andalcoholate reactants. The acylpyrazine ether product can be recovered byconventional means such as extraction with an organic solvent.

The halo-acylpyrazine intermediate recovered in step (3) of the processis a novel type of pyrazine derivative. Thus, in a further embodimentthe present invention provides a class of halo-acylpyrazines which canbe prepared by a process which comprises the steps of (1) providing aheterogeneous reaction medium consisting of a water-immiscible organicphase and an acidic aqueous phase, wherein the organic phase comprises amixture of a R--CHO aldehyde compound and a halopyrazine compoundcorresponding to the formula: ##STR6## where Y is a halogen atom, and R¹is a substituent selected from hydrogen and alkyl groups containingbetween about 1-6 carbon atoms, and R in the aldehyde compound is asubstituent selected from aliphatic, alicyclic and aromatic groupscontaining between about 2-12 carbon atoms; (2) maintaining efficientcontact between the organic and aqueous phases for a period of timesufficient to achieve acylation of the halopyrazine compound in thepresence of a free radical generating agent; and (3) recovering ahalo-acylpyrazine product corresponding to the formula: ##STR7## whereY, R and R¹ are as previously defined, with the proviso that theposition-(2) substituent is not hydrogen.

The halo-acylpyrazine product can be recovered by conventional methodssuch as extraction of the reaction product medium with an organicsolvent (e.g., methylene chloride) as illustrated in Example I. Thehalopyrazine starting materials can be prepared by suitable halogenationof the pyrazine structure. J. Agric. Food Chem., 23(4), 638(1975)describes the halogenation of alkylsubstituted pyrazine compounds withchlorine or sulfuryl chloride.

General procedures for the preparation of halopyrazines are described inpublications such as J. Am. Chem. Soc., 74, 1580(1952); J. Agric. FoodChem., 20, 682(1972); J. Org. Chem., 26, 2356(1961); J. Chem. Soc.,Perkin I, 2004(1972); and J. Org. Chem., 26, 2360(1961).

Preparation of Tobacco Compositions

The present invention smoking compositions can be prepared by admixingnatural tobacco and/or reconstituted tobacco and/or a non-tobaccosubstitute with between about 0.00001 and 2 weight percent, andpreferably 0.0001-2 weight percent, based on the weight of the smokingcomposition, of a flavorant additive which corresponds to one of thestructural formula set forth hereinabove in definition of theacylpyrazine ether compounds.

An invention acylpyrazine ether flavorant additive can be incorporatedinto the tobacco in accordance with methods known and used in the art.Preferably the flavorant additive is dissolved in a solvent such aswater, alcohol, or mixtures thereof, and then sprayed or injected intothe tobacco or non-tobacco substitute matrix. Such method ensures aneven distribution of the flavorant additive throughout the tobacco, andthereby facilitates the production of a more uniform smokingcomposition. Alternatively, the flavorant may be incorporated as part ofa concentrated tobacco extract which is applied to a fibrous tobacco webas in the manufacture of reconstituted tobacco. Another suitableprocedure is to incorporate the flavorant in tobacco or non-tobaccosubstitute filler in a concentration between about 0.5-5 weight percent,based on the weight of filler, and then subsequently to blend thetreated filler with filler which does not contain flavorant additive.

The term "non-tobacco substitute" is meant to include smoking fillermaterials such as are disclosed in U.S. Pat. Nos. 3,529,602; 3,703,177;3,796,222; 4,019,521; 4,079,742; and references cited therein;incorporated herein by reference.

Illustratively, U.S. Pat. No. 3,529,602 describes a burnable sheet whichmay be used as a tobacco substitute, which sheet contains ingredientswhich include (1) a film-forming ingredient comprising a pectinaceousmaterial derived from tobacco plant parts and having an acid value inexcess of 30 milligrams of potassium hydroxide per gram, and (2) amineral ingredient comprising an alkali metal salt, an alkaline earthmetal salt or clay.

U.S. Pat. No. 3,703,177 describes a process for preparing a non-tobaccosmoking product from sugar beet pulp, which process involves the acidhydrolysis of the beet pulp to release beet pectins, and at least analkaline earth treatment thereafter to cause crosslinking of the pectinsand the formation of a binding agent for the exhausted beet matrix.

U.S. Pat. No. 3,796,222 describes a smoking product derived from coffeebean hulls. The hulls are treated with reagents that attack the alkalineearth metal crosslinks causing the release of the coffee pectins. Thepectins act as a binding agent and together with the treated hulls maybe handled and used similarly to a tobacco product.

U.S. Pat. No. 4,019,521 discloses a process for forming a smokingmaterial which involves heating a cellulosic or other carbohydratematerial at a temperature of 150°-750° C. in an inert atmosphere for aperiod of time sufficient to effect a weight loss of at least 60 percentbut not more than 90 percent.

U.S. Pat. No. 4,079,742 discloses a process for the manufacture of asynthetic smoking product from a cellulosic material, which processinvolves a pyrolysis step and a basic extraction step to yield aresultant matrix which has a tobacco-like brown color and has improvedsmoking characteristics.

When a present invention acylpyrazine ether is incorporated into smokingmaterial as a flavorant additive, and cigarettes are manufactured fromthe flavored blend, under smoking conditions the cigarettes have afuller flavor amplitude and/or other desirable properties in comparisonwith control cigarettes which do not contain an invention acylpyrazineether flavorant additive, as demonstrated in Example VIII.

The following examples are further illustrative of the presentinvention. The reactants and other specific ingredients are presented asbeing typical, and various modifications can be derived in view of theforegoing disclosure within the scope of the invention.

EXAMPLE I Preparation Of 1-(3-Chloro-2-pyrazinyl)-1-propanone ##STR8##

To a stirring heterogeneous mixture of 2-chloropyrazine (1.14 g, 10mmoles) and freshly distilled propionaldehyde (3.48 g, 60 mmoles) in 5.5ml of 5.2 M sulfuric acid, at 3° C., is added concurrently 70% t-butylhydroperoxide (5.4 g, mmoles) 42 and a solution of ferrous sulfate (16.7g, 60 mmoles) in 40 ml of water over a 5 minute period. The resultingheterogeneous mixture is stirred an additional 1 hour during which timethe temperature is raised to 15° C. Solid sodium sulfite is then addeduntil test with starch-iodide paper is negative.

The aqueous mixture is extracted with methylene chloride (3×100 ml), andthe extracts are combined and washed with water. After drying (MgSO₄),the solvent is removed under reduced pressure to give 1.5 g of a crudeproduct mixture.

The product mixture is passed thru a silica gel column in 15%acetone/hexane, followed by preparative thick layer chromatography(2000μ silica gel GF, developed with 10% acetone/hexane) to provide a15% yield of 1-(3-chloro-2-pyrazinyl)-1-propanone.

An analytically pure sample is obtained by preparative GLC, and IR andNMR spectra confirm the structure.

EXAMPLE II Preparation of 1-(3-Ethylthio-2-pyrazinyl)-1-propanone##STR9##

A mixture of sodium ethoxide (100 mg, 1.47 mmoles) and ethanethiol (110mg, 1.77 mmoles) in 7 ml of absolute ethanol is stirred under nitrogenat room temperature for 10 minutes. 1-(3-Chloro-2-pyrazinyl)-1-propanone(250 mg, 1.47 mmoles) in 5 ml absolute ethanol is added to the abovemixture, and the reaction mixture is stirred for 4 hours at which timethin layer chromatography indicates that all of the starting materialshave reacted. The mixture is poured into water (100 ml) and extractedwith methylene chloride (3×10 ml), and the extracts are combined andwashed with water (1×50 ml) and saturated NaCl solution (1×50 ml). Afterdrying (MgSO₄), the solvent is removed under reduced pressure to give an87% yield of 1-(3-ethylthio-2-pyrazinyl)-1-propanone (m.p. 45°-48° C.).

An analytically pure sample is obtained by preparative GLC, and IR, NMRand MS spectra confirm the structure.

Anal. calc. for C₉ H₁₂ N₂ OS: C,55.08; H,6.18; N,14.09; S,16.47.

Found: C,54.91; H,6.16; N,14.27; S,16.34.

EXAMPLE III Preparation Of 1-(3-Chloro-2-pyrazinyl)-2-methyl-1-propanone##STR10##

To a stirring mixture of 2-chloropyrazine (5.0 g, 43.6 mmoles), freshlydistilled isobutyraldehyde (15.8 g, 218 mmoles), 65.5 ml of glacialacetic acid, 13.1 ml of concentrated sulfuric acid, and 65 ml of water,at about 5° C., is added ferrous sulfate (24.3 g, 87.4 mmoles) in 45 mlof water over a 10 minute period, followed by rapid treatment with 70%t-butyl hydroperoxide (11.2 g, 87 mmoles). The reaction mixture isbrought to room temperature and stirred for 1.5 hours. Solid sodiumsulfite is added until test with starch-iodide paper is negative. Afterextracting with benzene (3×100 ml), the combined extracts are washedwith saturated sodium bicarbonate solution (75 ml) and saturated brine(75 ml), and then dried (MgSO₄).

Following concentration, the resultant crude product is subjected todistillation (70°-145° C. at 0.2-0.1 mmHg) followed by columnchromatography (silica gel 60, eluted with 3% acetone/hexane) to providea 20% yield of 1-(3-chloro-2-pyrazinyl)-2-methyl-1-propanone.

An analytically pure sample is obtained by preparative GLC, and IR, NMRand MS spectra confirm the structure.

Anal. calc. for C₈ H₉ N₂ OCl: C,52.04; H,4.91; N,15.17; Cl19.20.

Found: C,51.92; H,4.94; N,15.06; Cl19.30.

EXAMPLE IV Preparation Of 1-(3-Methoxy-2-pyrazinyl)-2-methyl-1-propanone##STR11##

To a stirring solution of 1-(3-chloro-2-pyrazinyl)-2-methyl-1-propanone(513 mg, 2.78 mmoles) under nitrogen at about 5° C. is added 8.8 ml 0.35M sodium methoxide solution (165 mg, 3.06 mmoles). The bright yellowsolution is stirred at room temperature for 1 hour and then refluxed for1.5 hours, and GLC analysis indicates a complete reaction.

The mixture is diluted with 75 ml of water, followed by extracting withdiethyl ether (3×75 ml) and washing of the combined ethereal layers withwater (50 ml) and saturated brine (50 ml). After drying (MgSO₄), thesolvent is removed under reduced pressure to provide a quantitativeyield of 1-(3-methoxy-2-pyrazinyl)-2-methyl-1-propanone.

An analytically pure sample is obtained by preparative GLC, and IR, NMRand MS spectra confirm the above structure.

Anal. calc. for C₉ H₁₂ N₂ O₂ : C,59.99; H,6.71; N,15.54.

Found: C,59.93; H,6.88, N,15.78.

The structure of the product compound (i.e., the 2,3-disubstitution) isproved by reacting the compound with NaBH₄ to give an alcohol which isfound to be identical to that obtained by oxidizing the known2-methoxy-3-isobutylpyrazine.

EXAMPLE V Preparation Of1-(3-Furfurylthio-2-pyrazinyl)-2-methyl-1-propanone ##STR12##

A mixture of sodium ethoxide (148 mg, 2.18 mmoles) and furfurylmercaptan (285 mg, 2.50 mmoles) in 8 ml of absolute ethanol is stirredunder nitrogen at room temperature for 20 minutes.1-(3-Chloro-2-pyrazinyl)-2-methyl-1-propanone (400 mg, 2.17 mmoles) in 4ml of absolute ethanol is then added to the reaction medium, and thereaction medium is stirred for 2 hours. Thin layer chromatography(silica gel GF, 20% acetone/hexane) indicates complete reaction, and themixture is then poured into 100 ml of water. After extracting withmethylene chloride (3×100 ml), the combined extracts are washed withsaturated sodium bicarbonate (50 ml) and with saturated sodium chloride(50 ml). After drying (MgSO₄), the solvent is removed under reducedpressure to give 450 mg of crude product.

Column chromatography (silica gel 60, eluted with 10% acetone/hexane)followed by crystallization from hexane provides a 32% yield of1-(3-furfurylthio-2-pyrazinyl)-2-methyl-1-propanone as yellow needles(m.p. 57°-58° C.). The structure of the product compound is confirmed byIR, NMR and MS spectra.

Anal. calc. for C₁₃ H₁₄ N₂ O₂ S: C,59.52; H,5.38; N,10.68; S,12.22.

Found: C,59.77; H,5.40; N,10.79; S,12.37.

EXAMPLE VI Preparation Of1-(5-Chloro-3,6-dimethyl-2-pyrazinyl)-1-propanone ##STR13##

The reaction of 2-chloro-3,6-dimethylpyrazine and propionaldehyde isconducted on a 0.05 mole scale as described in Example III, with theexception that hexane is used as the extracting solvent.

Short path distillation (60° C. at 0.1 mm Hg) affords a 68% yield of1-(5-chloro-3,6-dimethyl-2-pyrazinyl)-1-propanone.

An analytically pure sample is obtained by preparative GLC, and IR, NMRand MS data confirm the structure.

Anal. Calc. for C₉ H₁₁ N₂ OCl: C,54.42; H,5.58; N,14.10; Cl,17.85.

Found: C,54.54; H,5.57; N,14.23; Cl,18.04.

EXAMPLE VII Preparation Of1-[3,6-Dimethyl-5-(cis-hex-3-enoxy)-2-pyrazinyl]-1-propanone ##STR14##

cis-3-hexenol (4 ml) is slowly added to solid sodium hydride (114 mg,4.75 mmoles) under nitrogen at ˜5° C. After the addition is completedand the gas evolution has subsided, the mixture is stirred for 30minutes at 5°-10° C. 1-(5-Chloro-3,6-dimethyl-2-pyrazinyl)-1-propanone(750 mg, 3.78 mmoles) in 1 ml of cis-3-hexenol is added and the reactionmixture is stirred for 3 hours at room temperature. The resultantproduct mixture is quenched with water and extracted with diethyl ether(3×25 ml), and the combined extracts are washed with water (20 ml).

After drying (MgSO₄), the solvent is removed under reduced pressure andexcess cis-3-hexenol is removed by bulb-to-bulb distillation (oven temp.50° C. at 0.05 mmHg). A quantitative yield of1-(3,6-dimethyl-5-(cis-hex-3-enoxy)-2-pyrazinyl)-1-propanone isobtained.

An analytically pure sample is obtained by preparative GLC, and IR, NMRand MS spectra confirm the structure.

Anal. calc. for C₁₅ H₂₂ N₂ O₂ : C,68.67; H,8.45; N,10.68.

Found: C,68.74; H,8.23; N,10.66.

EXAMPLE VIII Preparation of Present Invention Smoking CompositionsContaining a Novel Acylpyrazine Ether Flavorant

Cigarettes fabricated to deliver 8 mg of tar using a typical blend oftobaccos are treated with an ethanolic solution of an acylpyrazine etherflavorant as listed in the Table, with the indicated ppm of the compoundby weight of the tobacco. Untreated control cigarettes are preparedusing the identical tobacco blend and spiked with unflavored ethanol,and the treated cigarettes are compared to the controls by anexperienced smoking panel.

Each subjective evaluation involves a set of three cigarettes, two ofwhich are unflavored control cigarettes, and the third is one treatedwith a flavorant.

The flavorant-treated cigarettes are found to have the smoke flavorproperties described in the Table, as compared to the controls.

                                      TABLE                                       __________________________________________________________________________                                                SMOKE FLAVOR                      EXAMPLE                                                                              COMPOUND            PPM                                                                              ODOR          PROPERTIES                        __________________________________________________________________________    II                                                                                    ##STR15##          314                                                                              Sharp, caramel, roasted, musty, earthy,                                       cabbage       Smoother, light sweet apple                                                   note, slight burnt phenolic       IV                                                                                    ##STR16##          370                                                                              Green, sharp, vegetable, isovaleric acid                                      character     Green-sour, fuller                        ##STR17##          400                                                                              No aroma at room tempera- ture, roasted                                       meat when heated                                                                            Fuller, dry-roasted peanut                                                    husk, smoother                    VII                                                                                   ##STR18##          360                                                                              Sweet, green, roasted, caramel                                                              Green caramel                     __________________________________________________________________________                                                note                          

What is claimed is:
 1. An acylpyrazine ether corresponding to theformula: ##STR19## where R is a substituent selected from aliphatic,alicyclic and aromatic hydrocarbyl groups having 2-12 carbon atoms, R¹is a substituent selected from hydrogen and alkyl groups having 1-6carbon atoms, X is etheric oxygen or sulfur, and R² is a substituentselected from aliphatic, alicyclic and aromatic hydrocarbyl groupshaving 1-12 carbon atoms, with the proviso that the position-(3)substituent is not hydrogen.
 2. 1-(3-Ethylthio-2-pyrazinyl)-1-propanone.3. 1-(3-Methoxy-2-pyrazinyl)-2-methyl-1-propanone. 4.1-(3-Furfurylthio-2-pyrazinyl)-2-methyl-1-propanone. 5.1-[3,6-Dimethyl-5-(cis-hex-3-enoxy)-2-pyrazinyl]-1-propanone.
 6. Ahalo-acylpyrazine corresponding to the formula: ##STR20## where Y is ahalogen atom, R is a substituent selected from aliphatic, alicyclic andaromatic hydrocarbyl groups having 2-12 carbon atoms, and R¹ is asubstituent selected from hydrogen and alkyl groups having 1-6 carbonatoms, with the proviso that the position-(2) substituent is nothydrogen.
 7. 1-(3-Chloro-2-pyrazinyl)-1-propanone. 8.1-(3-Chloro-2-pyrazinyl)-2-methyl-1-propanone. 9.1-(5-Chloro-3,6-dimethyl-2-pyrazinyl)-1-propanone.
 10. Ahalo-acylpyrazine corresponding to the formula: ##STR21## where Y is achlorine atom, R is a substituent selected from aliphatic, alicylclicand aromatic hydrocarbyl groups having 2-12 carbon atoms, and R¹ is asubstituent selected from hydrogen and alkyl groups having 1-6 carbonatoms, with the proviso that the position-(2) substituent is nothydrogen.
 11. A halo-acylpyrazine corresponding to the formula:##STR22## where Y is a bromine atom, R is a substituent selected fromaliphatic, alicylclic and aromatic hydrocarbyl groups having 2-12 carbonatoms, and R¹ is a substituent selected from hydrogen and alkyl groupshaving 1-6 carbon atoms, with the proviso that the position-(2)substituent is not hydrogen.